Method of treating fabrics

ABSTRACT

There is disclosed a process comprising treating textile materials containing thermoplastic fibers with an aqueous emulsion containing approximately by weight (I) 5 to 15% of a graft copolymer of a poly (N-vinyl lactam) of the formula:   WHEREIN R represents an alkylene bridge group necessary to complete a 5,6 or 7-membered heterocyclic ring system, R&#39;&#39; represents either hydrogen or a methyl group, and n represents a number indicative of the extent of polymerization and is usually at least 3 or 4; having graft polymerized thereon at least one member selected from the group, consisting of C1 6 alkyl acrylates, acrylic acid and N-alkylol acrylamides and methacrylamides, (II) 0 to 3% of a crosslinking agent, (III) 0 to 5% of a cationic softener and (IV) 95 to 80% water; and thereafter subjecting the treated materials to curing conditions.

United States Patent Sthare et a1.

[ Oct. 7, 1975 METHOD OF TREATING FABRICS [75] lnventors: Derwin K. Sthare, Charlotte;

William T. Ledford, Gastonia, both of NC.

[52] US. Cl. 8/1157; 8/1156, 8/189; 117/1388 A; 117/1388 F',117/138.8 N;

117/1388 UA; 117/1395 A; 260/296 RW;

260/296 HN; 260/296 RB; 260/875; 260/885 [51] Int. Cl D06m 15/52 [58] Field of Search 117/1395 A, 138.8 A, 117/1388 F,138.8 N;8/l15.7,189, 115.6; 260/885 [56] References Cited UNITED STATES PATENTS 3,166.525 1/1955 Perry 117/1395 X 3,244,658 4/1966 Grosser et a1 260/885 X 3,402,987 9/1968 Dalton et a1. 117/1395 X 3,475,581 11/1969 Weitzel et a1... 117/62 3,483,024 12/1969 Roff 117/1395 3,536,650 10/1970 Jasinski et a1 i 260/296 3,749,691 7/1973 Kandathil 117/1395 X Primary ExaminerHerbert B. Guynn Attorney, Agent, or Firm-Walter C. Kehm; Joshua J. Ward 57 ABSTRACT There is disclosed a process comprising treating textile materials containing thermoplastic fibers with an aqueous emulsion containing approximately by weight (1) 5 to 15% of a graft copolymer of a poly (N-vinyl lactam) of the formula:

wherein R represents an alkylene bridge group necessary to complete a 5,6 or 7-membered heterocyclic ring system, R represents either hydrogen or a methyl group, and n represents a number indicative of the extent of polymerization and is usually at least 3 or 4; having graft polymerized thereon at least one member selected from the group, consisting of C alkyl acrylates, acrylic acid and N-alkylol acrylamides and methacrylamides, (ll) 0 to 3% of a crosslinking agent, ([11) 0 to 5% of a cationic softener and (IV) 95 to 80% water; and thereafter subjecting the treated materials to curing conditions.

8 Claims, N0 Drawings METHOD OF TREATING FABRICS BACKGROUND OF THE INVENTION This invention relates to a process for rendering thermoplastic fiber-containing textile materials normally succeptible to snag, picking, and pull damage, resistant to such damage. The process includes contacting said material with a pad bath emulsion containing a poly (N-vinyl lactam)'graft copolymer.

Knitted fabrics, particularly those of double knit construction and/or those employing texturized yarn, show a tendency to snag or pull. Snagging is a particulaly acute problem in mens clothing where the retail price of the goods is quite high and a garment repeatedly damaged by snagging eventually becomes unattractive and/or unwearable and thus makes the price-life of the garment prohibitive.

Various suggestions have been made in the prior art to solve these problems and various types of articles are offered on the market which are resistant to the aforesaid difficulties by the adoption of other than plain knit structure, for example, through the use of tuck stitches or draw stitches involving the knitting of different parts of a textile article of two different yarns. In such an article resistance to pulling, snagging and picking may be accomplished by use of one plain knit stitch and another special stitch may be produced. To the greater majority of wearers these textile articles are unacceptable for general use because of the appearance of the garments.

Chemical and adhesive treatments have been utilized in the prior art to overcome the difficulties of pulling, snagging and picking in woven and knitted fine dinier sheer garments. None of these treatments have been really commercially successful because any treatment that is proven to be effective will affect the hand and/or the stretch characteristics of the garments. These treatments are reputed to reduce snagging and produce a finish highly durable to both washing and dry cleaning. The finishes employed include straight acrylates or modifications thereof (US. Pat. Nos. 3,476,581; 3,483,024 and 3,567,498), such as a poly- (ethyl acrylate); one such typical example being Vibraflex MF"; and poly (acrylates) combined with a filler, such as, Mace Guard 702". Problems associated with straight acrylate finishes include shade change on dyed fabrics, wet crocking, a stiffer hand and a significant reduction of wash fastness of certain dyes.

Poly acrylates as above-employed also have other drawbacks, including a stiff hand when the surfactant is leached out of the emulsion during washing of the treated material; lack of moisture regain after washings and the like.

It is to be understood that the emulsion additive" of the instant invention is not chemically the same nor does it function as an adjunct to improve hand" and abrasion resistance of resin treated textiles. In other words, the instant emulsion will not be applied along with permanent press" finishes to modify hand or improve abrasion resistance of said pemanent press finishes. The instant emulsion is therefore not employed as an additive or coreactant in the production of durable press garments produced by the application and subsequent curing of thermosetting resins to the fabric. The emulsion therefore is not employed in the endeavor to improve the abrasion rsistance of such fabrics as said term is known in the art. Improving the abrasion resistance of durable press resin treated textiles refers to the wear that occurs at the sleeve cuffs, pant cuffs and shirt collar. Said term does not generically include snagging and pulling as is known in the art to occur specifically to knitted materials, double knits and warp knits-of polyester, acrylates and nylon materials. Accordingly, where knitted articles, particularly those of double knit construction, have shown a tendency to snag on sharp or pointed objects, treatment with a durable press resin finish cannot be employed to prevent snagging and pulling, notwithstanding the fact that other resin treated fabrics might be more resistant to abrasion by treatment therewith.

SUMMARY OF THE INVENTION It is an object of the instant invention to provide a process for rendering textile materials containing thermoplastic fibers normally susceptible to snag, picking and pull damage less susceptible thereto while still retaining excellent hand" and stretch characteristics.

It is also an object of this invention to develop a finish that will significantly reduce the tendency to snag, pick and pull wherein the finish can be applied by a fabric finisher in a simple and practical manner.

It is another object of the instant invention to provide a thermoplastic fiber containing textile material so treated.

it is yet another object of the instant invention to carry out the above mentioned process employing an emulsion containing agraft copolymer of a poly(N- vinyl lactam) having grafted thereon at least one member derived from the group consisting of C1. g alkyl acrylate esters, acrylic acid and an N-alkylol acrylamide or methacrylamide.

It is a further object of the instant invention to avoid one or more drawbacks of the prior art.

Other objects and advantages will appear as the description proceeds.

In satisfaction of these foregoing objects and advantages, there is provided by this invention a process for rendering thermoplastic fiber-containing materials more resistant to picking, snagging and pulling, comprising treating same at a temperature between about 50F and l25F with an aqueous emulsion containing approximately by weight (I) 5 to 15% of a graft copolymer of a poly(N-vinyl lactam) having an average molecular weight between about 400 and about 2,000,000 and having the formula CH CH2 wherein R represents an alkylene bridge group of 2 to 4 carbon atoms necessary to complete a 5,6 or 7- membered heterocyclic ring system, R, represents either hydrogen or an alkyl group, and n represents a number indicative of the extent of polymerization, having graft polymerized thereon at least one member derived from the group consisting of C alkylacrylate esters, acrylic acid and an N-alkylol acrylamides or methacrylamides, said graft copolymer having a weight ratio of poly (N-vinyl lactam) to comonomer of between about 1 to 4 and 3.5 to l. (II) 0 to 3% of an acid cross linking agent, (Ill) to of a cationic softener; and (IV) 95 to 80% water. The treated material is thereafter subjected to curing conditions whereupon there remains on said material approximately 2 to 4% by weight of said graft copolymeric emulsion.

The polymeric N-vinyl lactams utilized in the preparation of the graft copolymer of this invention are characterized by the following general structural formula R R, CH CO l cu CH,

wherein R and R are as above defined and n is usually at least 3 or 4.

All of the specific polymeric materials characterized by the foregoing general formula are commercially available and called polymeric N-vinyl lactams. They are obtained by polymerizing organic 5,6 or 7- membered ring compounds containing in their rings the NH CO group, such as, for example, l-vinyl-Z- pyrrolidone, 1-vinyl-5-methyl-Z-pyrrolidone, l-vinyl-2- piperidone, N-vinyl-e-caprolactam, and the like. Depending upon the extent of polymerization, they have molecular weights ranging from at least 400 up to 2,000,000 or more. Viscosity measurements are commonly used as an indication of the average molecular weight of polymeric compositions the instant polymers being characterized by a chain of carbon atoms to which the lactam rings are attached through their nitrogen atoms:

CH-CH., H-CH,

The K value (Fikentscher) of any particular mixture of polymers is calculated from viscosity data and is useful as an indication of the average molecular weight of such mixture. its determination is fully described in Modern Plastics, 23, No. 3, l576l,2l2,2l4, 216, 218 (I945), and is defined as 1000 times k in the empirical relative viscosity equation:

wherein C is the concentration in grams per hundred cc. of polymer solution and "rel is the ratio of the viscosity of the solution to that of pure solvent. The K values are reported as I000 times the calculated viscosity coefficient in order to avoid the use of decimals. For the purpose of the present invention, there may be employed those polymeric N-vinyl lactams having a K value of about 10 to 200, preferably of 30 to 100 because of their viscosity at lower concentrations.

K values and specific viscosities (n,,,) are interconvertible and are related through relative viscosity (1rrel). Thus, when viscosity measurements are taken on solutions which have a concentration of 1.00 gram of polymer per deciliter of solution at 25C (C=l the relationships are as follows:

Relative viscosity specific viscosity plus one. Relative viscosity IO [0.00 l K+0.000075K H00 I 5K) Hence,

-n,,,=1=l0[0.00lK+ 0.000075K /(l 0.001510]. Relative viscosity, specific viscosity and K are dimensionless, whereas inherent viscosity (log M C and intrinsic viscosity (the limit of inherent viscosity as C approaches zero) have the dimensions of dilution, i.e., the reciprocal of concentration. lntrinsic viscosity and K are intended to be independent of concentration.

The number of recurring polymer units enclosed by brackets in the foregoing general structural formula, indicated by n, or the extent of degree of polymerization, corresponds to a chain of roughly 4 to 20,000 monomer units or more. ln actual practice, a mixture of polymeric molecules, each containing a different number (n) of monomer units, is produced. The polymers are readily prepared by the procedural steps taught in US. Pat. Nos. 2,265,450, 2,317,804, 2,335,454, 3,244,658. and 3,536,650 and in which working examples of the species characterized by the above formula are given, all of which patents are incorporated herein by reference.

The alkyl acrylates which are employed in the invention are those alkyl esters of acrylic acid wherein the alkyl portion contains about 1 to about 12, preferably 1-6 carbon atoms. The alkyl chain may be a straight or branched chain. Particularly preferred compounds falling within this class are ethylacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like. Mixtures of these acrylates may also be employed. These compounds are well known to the art.

The N-alkylol amides having the formula:

wherein R is hydrogen or methyl, R is hydrogen or C alkyl, aralkyl and aryl and R is hydrogen or C alkyl or cycloalkyl of an a,B-olefinically unsaturated carboxylic acid including those having from 4 to 10 carbon atoms; exemplary amides include N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-ethanol methacrylamide, and the like. The preferred monomers of the N-alkylol amide type because of their ready availability and relative low cost are the N-alkylol amides of afi-monoolefinically unsaturated monocarboxylic acids and the most preferred are N-methylol acrylamide and N-methylol mechacrylamide.

The acrylic acid monomeric units are derived from an a,B-unsaturated acid of the formula:

wherein R is hydrogen or an alkyl group of l to about 7 carbon atoms. Illustrative of such compounds are acrylic acid and methacrylic acid as well as those acids wherein R is an alkyl group of 2 to 7 carbon atoms. These compounds and their methods of preparation are well known in the art. Acrylic acid is especially preferred because of its ready availability and the excellent properties of the products obtained therefrom.

While not wishing to be bound by any particular theory or mechanism of reaction, it is believed that the arrangement of the monomeric units, that is, the alkyl acrylate, acrylic acid and N-methyl amide units is essential in relation to the polymeric N-vinyl lactam. With respect to the graft copolymers of the present invention, said monomeric units are not situated in the main polymer chain but rather they form a more or less alternating side chain on the performed poly N-(vinyl lactam) which forms the skeletal chain for the addition of said units. Thus the polymers may be characterized as graft copolymers.

The comonomers that are useful in this invention include those which cross-link or cure to form a relatively soft film. These monomers should combine softness, resilience and low temperature flexibility with improved wash fastness. They should be cross-linkable, which means that they should either be self crosslinking or capable of reacting or curing in situ with a nitrogeneous or other type of external cross-linking agent, under the curing conditions of this invention set forth hereinafter. The compound or compounds having groups that are capable of cross-linking may be reacted in situ during the curing step of this procedure if desired, to form a thermosetting type resin.

It is to be understood that the poly(N-vinyl lactam) substrate being of hydrophilic nature, water soluble and having the ability to absorb moisture from the environment, significantly enhances the aforementioned polymeric finish and as such, the properties of the fibers so treated.

The aforesaid cross-linking component (i.e., N- alkylol amides) is operative to lock into both the substrate and the hydroxyl groups of cellulosics where polyester blends are employed; the foregoing, notwithstanding the fact that said substrate is water soluble. In those finishes employing a crosslinking agent with a straight acrylate the finish gradually leaches out each time the fiber is washed.

The process of the present invention may be applied to knitted or woven fabrics and also to fabrics or articles containing wool and/or nylon in admixture with other fibers such as the synthetic protein fibers, cotton, rayon, casein fiber and cellulose acetate.

Among the articles which may be treated according to the present invention are underwear, or outerwear garments, hose, socks and stockings, felts, hats, ties, furnishing fabrics, upholstery, gloves, scarves, curtains, etc.

The process of the invention may be applied to a dyed or undyed material. In the case of the undyed material the dyeing may be effected during the process of the present invention or may be effected subsequent to this treatment. If is, however, preferable that the textile materials treated in accordance with this invention should be free of other finishes, i.e., lanolin lubricants or the like.

The fabrics or articles treated in accordance with this invention show an increased resistance to picking, snagging and pulling.

The term picking" as used herein refers to the tendency of fabric to have unsightly broken threads and holes, this characteristic being particularly present in knitted goods. The measurement of this physical characteristic of fabrics can be carried out on the Hanes Pick Tester, US. Pat. No. 3,044,293. This tester comprises a small cylindrical tumbling device equipped with baffles and with a number of straight pins protruding from the cylinder wall. In the use of this pick testing device the goods are first inspected and all defects marked and then put into the pick tester and tumbled. The instant process of applying said finish to such goods, is particularly effective on garments produced from textured textile yarn, polyester knits, polyester double-knits, warp kints, and polyester blends used in knit goods. The finish, when applied to the goods, shows a definite ability to reduce snagging and to permenantly modify the hand of the fabric, thus making the fabric particularly attractive for menswear. The finish may be applied at various levels for durable hand building of the fabric and/or to provide varying degrees of anti-snag characteristics.

DETAILED DESCRIPTION The emulsions prepared and used in accordance with the instant invention have been found to be homogeneous, stable, aqueous emulsions containing a graft copolymer of a polymeric N-vinyl lactam having grafted thereon units of an acrylic acid ester, i.e., ethyl or butyl acrylate and an N-alkylol amide; a graft copolymer containing only a lower alkyl acrylate such as the above graft polymerized on the poly (N-vinyl lactam) or a graft copolymer containing units of said acrylic acid graft polymerized on said poly (N-vinyl lactam) as substrate and like graft copolymers. The emulsions are prepared, for example, in accordance with the teachings of the aforesaid patents. They are characterized by unusually good stability, low to medium viscosities, the ability to deposit a clear transparent film on a glass plate and a polymeric product which is essentially water insoluble and at least about soluble in aromatic solvents, i.e, benzene. The emulsions are further characterized by the ability to be converted to a thermosetting product by heating with an acid or acid salt such as zinc nitrate and the like to about to l80C for l hour to 1 minute respectively.

The ratio (by weight) of the polymeric N-vinyl lactam and the comonomers can generally range from about 1 to 4 to about 3.5 to l. In a preferred embodi ment the copolymeric product will contain not more than about 60 70% polymeric N-vinyl lactam and at least 30% of one of said monomeric units. More specific preferred embodiments include those in which graft copolymers include 20 49 weight percent poly N-vinyl pyrrolidone, 50 70% ethylacrylate and 0. l to 10 weight percent acrylic acid as well as those which include 20 40 weight percent poly N-vinyl pyrrolidone, 50 70 weight percent C alkyl acrylate and O.l 10 weight percent N-methylol acrylamide.

In order to effect cross-linking of the polymer and in order to accomplish good adhesion to the fabric or garment substrate, it is necessary where an n-alkylol amide is not employed to add a cross-linking agent to the aqueous emulsion. Suitable cross-linking agents are well-known in the textile arts. Suitable acid crosslinking agents include oxalic, succinic, adipic, and citric acid. The acid most frequently used is oxalic acid.

The acid cross-linking agent, when employed, is used in amounts up to 3% on the weight of the graft copolymer, preferably 0.5 to l.5%.

It should be understood that any of the well-known lubricants that are conventionally used to faciliate subsequent processing of fabrics may be added to the polymeric emulsions so long as they are compatible therewith. Likewise, antifoaming agents and other additives that do not affect the hand," stretch or other desirable characteristics of the fabric or garment may be added to the emulsion.

The polymeric material described above is utilized in a water base emulsion as the treatment medium in accordance with this invention. The polymer may be present in an amount ranging from about 5 to l5% by weight, based upon the weight of the aqueous emulsion. [n the preferred embodiment of this invention the polymeric material will preferably be present in the emulsion in the approximate range of 7 to 12% by weight, based upon the weight of the emulsion. Where a viscosity improver can be utilized to obtain a more uniform emulsion a higher content can be used.

The emulsion may contain to 3.5% of a softener based on the weight of the fabric, this depending on the particular polymeric emulsion used and the desired hand of the finished product. Suitable softners include Gaftex E -a polyethylene emulsion; Gaftex SC-300 a cationic modified amide; Gafstat AD-S l0-a free acid of a complex phosphate ester; Gafac RM-7l0-a phosphate ester with an aromatic hydrophobic base; Cutless 50 a blend of polyethylene and cationic softners and the like.

As previously stated, in those embodiments where an N-alkylol amide is not employed there is needed a cross-linking agent such as a dicarboxyclic acid, eg. oxalic acid. It is believed that the N-alkylol amide functionality is operable to internally cross-link with the cotton, where cotton/polyester blends are treated, and where a latent acid such as zinc nitrate or magnesium chloride is utilized as a catalyst to promote such reaction.

The process of applying the emulsion may be carried out with existing plant equipment, such as a pad box and roll and drying frames.

Broadly speaking, the process comprises applying the emulsion to the material from a pad bath, the emulsion is padded onto, e.g., polyester fiber such that there is approximately 75l007z wet pick up thereon.

After cure, there should remain about 0.1 to preferably 2-47: grafted polymeric product by weight on the dry weight of the fabric. The pad bath temperature should he ambient to about 120F The drying and curing temperatures are about 250 to about 350F. The curing time will be approximately 30 seconds where the temperature is about 310F, greater time being required for lesser temperatures and lesser time being required at the higher temperatures.

In the usual procedure the aqueous emulsion is applied to the fabric or material. For example, a number of materials may be placed in a suitable container that is designed for a liquid treatment of this nature, and the articles or materials dipped and preferably submerged in the emulsion bath for a period of time ranging from a few seconds to five minutes or more. The emulsion bath may be at room temperature or at a temperature ranging from about 50F to l25F. After the textile article has been subjected to this treatment for a required length of time the article is placed in an extractor for the purpose of extracting the excess liquid emulsion that may remain thereon. This extractor may comprise a spin dryer, for example. It should be understood that other means for applying the emulsion of this invention may be utilized, for example, spraying, padding or the like. Subsequent to extraction, the material is preferably air dried for a period of time ranging approximately from an hour to 24 hours. At the end of this period the polymeric material will usually be present on the material or fabric in a weight percentage varying from about 0.1 to l5%, based on the weight of the material or fabric. During this period of time, due to the catalytic initiator present in the emulsion, some curing or crosslinking will take place. It is preferable, though not absolutely necessary, that some curing take place in this stage so that subsequent treatments of the material or fabric may be facilitated, without adhesion of the materials or fabric to the processing equipment.

In an alternative procedure and the one which is preferred for use in accordance with this invention, materials are allowed to dry after treatment with the above described emulsion and extraction for a sufficient period of time to effect the partial cure of this polymeric material.

The final result is a finished fabric having a desirable hand, light fasteness, durability and other good fabric qualities. These and other properties may be determined by tests known in the trade. It is to be understood that the emulsion is equally as effective on warp knit and stretch wovens as it is on double knit polyesters. Also included are the Ban-Ion" texturized nylon fabrics and Acrilon" acrylate fabrics as well as rayonpolyester blends.

The following examples are only illustrative of the instant invention; they are in no way to be considered as limiting. All parts and portions given therein as well as in the appended claims are by weight unless otherwise specified.

EXAMPLE 1 Grams Distilled water 220 Butyl acrylate l60 N-methylol acrylamide (607 active) 4 60 grams of the phosphate ester of nonyl phenol disclosed in Example l4 of US. Pat. No. 3,004,056.

Grams Ammonium persulfate 0.05 Sodium acetate 0.3 Aerosol OTtdialkyl sodium sulfosuccinate) 1.0

The mixture was agitated, purged with nitrogen and heated to C over a 30 minute period. At this time a mildly exothermic reaction ensued and cooling was necessary. The 70 temperature was maintained for three hours after which time the temperature was raised to C and a solution of 0.3 gram ammonium persulfate in 10 grams distilled water was added to complete the polymerization. One half hour later, the emulsion coagulated. See US. Pat. No. 3,536,650 for further details, said details incorporated herewith by reference.

EXAMPLE 11 Time Tcmp.,C Comments 9:39 24 Heating to reflux. 10:04 91 Refluxing, adding 90gms. ethyl acrylatc continuously over a 1 hour period. 1 1:04 90 All ethyl acrylate in, maintaining reflux until 100C 2:00 100 Cooling down. added 03ml. NH.,OH

and discharged.

Further details can be gleaned from US. Pat. No. 3,244,658 which is incorporated herein by reference.

EXAMPLE 111 Equipment same as in Example I. The ingredients of the polymerization are follows:

431.0 grns. distilled water I 15.2 gms. poly(vinyl pyrrolidone) 240.0 grns. Surfactant (L% solution of sodium lauryl sulfate) 160 gms. Ammonium persulfate solution) 263.4 gms. ethyl acrylate 5.4 gms. acrylic acid (1.4% based on the total amount of polymer) The distilled water is placed in the resin kettle equipped with the mechanical stirrer. reflux condenser, thermometer and gas inlet tube. The poly(vinyl pyrrolidone). and sodium lauryl sulfate surfactant are added, and the mixture is stirred until a clear solution is obtained. The system is then purged well with nitrogen gas and heating is started. At 60C 16 grams ammonium persulfate solution is added and the temperature is raised to 100C. This temperature is held for 30 minutes, then the mixture is cooled to 90C. At this temperature the addition of a mixture of ethylacrylate and acrylic acid is started. The addition takes place in three hours. At this point 1 gram of 1% ammonium persulfate is added. The addition of the catalyst is repeated every 2 hours until the amount of the unreacted monomers is below 0.1%. Finally the pH of the product is adjusted to 6.0 by the addition of concentrated ammonium hydroxide solution. (60% PVP/3439% acrylic acid ester 1-6 acrylic acid).

Analysis of resulting solution:

Solids: 35-27! Residual monomer: Nil Conversion: I007: K-value: 107.6 (in DMF) Brookfield viscosity: 50.2 cps pH (as is): 2.1

EXAMPLE IV The apparatus for the reaction is similar to that described in Example l. The ingredients of the polymerization are as follows:

1681.0 grams distilled water 449.3 grams poly(viny1 pyrrolidone) (K-30) 936.0 grams surfactant (10% solution of potassium lauryl sulfate) 988.3 grams ethyl acrylate 60.0 grams acrylic acid (4% acrylic acid based on total amount of polymer) 62.4 grams ammonium persulfate (5% solution) EXAMPLE V Application of the Emulsion to the fabric.

(Pad bath formulation preparation) Poly( Vinyl Pyrrolidone/Ethyl Acrylate) (30:70) 100 gms. Oxalic acid 1.0 gms. Gaftex E" cationic polyethylene emulsion 20-40 gms. Water 1000 gms.

The pad bath is heated to l20F and padded onto the fabric with the pad roll pressure adjusted to obtain wet pick up. The padded fabric is then dried and cured for 1-2 minutes at temperatures from 250350F; the time should be adjusted so that the fabric temperature equalizes ambient temperature in the final curing stage.

EXAMPLE Vl (Pad hath formulation modification) Poly( Vinyl Pyrrolidone/Ethyl Acrylatc/Acrylic Acid) 100 gms. Glycol(e.g. ethylenepropylene. l 4dibromobutanediol) 1-2 gms. Softener(OptionaLdepending on hand desired) 20-40 gms. Water, sufficient to make 1000 gms.

Procedure: Same as in Example V.

EXAMPLE Vll Components A B C D Poly( vinyl pyrrolidone/hydroxy ethyl acrylatc) 10.0 g 10.0 g. Poly(vinyl pyrrolidone/butyl 10 g 10 g.

acrylate plus 5% methylolacrylamide) Water g. 90 g 90 g. 90 g. Citric Acid 0.] g. 0 1 g 0.1 g. 0.1 g Magnesium Chloride 0.6 g. 0.6 g.

All pad baths are heated to 120F and applied at 100% wet pick-up on broadcloth cotton and 65/35 polyester cotton. All finishes are pre-dried at 250F for minutes before the final cure.

Finishes A & C are cured for 12 minutes at 325F in an attempt to cross-link the finish directly to the cotton. Finishes B & C (no magnesium chloride) are cured for 2 minutes at 325F in an attempt to cross-link the finish internally without cross-linking to the cotton.

Shrinkage tests are run by boiling the fabrics for minutes, rinsing, extracting and steam pressing to dryness. 10 inches X 10 inches swatches are used and a 5 inches square is measured off and marked in the center of each swatch just prior to boiling. The results are as follows:

Broadcloth Cotton 65/ 35 Polyester/Cotton A 5"X414/16" 5"X4 14/16" B 4 14/16" X4 14/16" 5" X4 14/16" D 5" X4 26/32" 4 31/32" X 414/16" Control 5' X412/16" 5" X 412/16" COMPARATIVE EXAMPLE Performance tests were run with the finish of Example l and two competitive products, Vibraflex MF and Mace Gard 702.

without departing from the spirit and nature of the invention, it is to be understood that all such changes and modifications are included within the scope of the invention.

We claim:

1. A process comprising treating textile materials containing thermoplastic fibers at a temperature between about F and about 125F with an aqueous emulsion containing approximately by weight (1) 5 to 15% of a graft copolymer containing approximately by weight 0.1 to 10% N-methylol acrylamide and 50 to of C alkyl acrylate graft polymerized on 20 to 40% of a poly (N-vinyl lactam) having an average molecular weight between about 400 and about 2,000,000 and having the formula wherein R represents an alkylene bridge group necessary to complete a 5, 6 or 7-membered heterocyclic ring system, R represents either hydrogen or a methyl group, and n represents a number indicative of the extent of polymerization (ll) 0 to 5% of a cationic softener based on the weight of the fibers being treated, and (Ill) to 80% water; and thereafter subjecting the treated materials to curing conditions including a tem- Evaluation/Finish Finish Ex.l Mace-Gard Vihrallex MF Application 9% OWF 3.0 3.0 3.0

(All finishes dryed at 250F, and cured at 350F for 30 seconds.)

Fabrics are evaluated using a l5 scale graduated as follows:

1. Severe change, 2. marked change, 3. moderate change,

4. slight change, 5. negligible or no change. The same double-knit texturized polyester was used in all above tests, dyed at a 2.0% level with GENACRON Blue BRL.

Since it is obvious that numerous changes and modifications can be made in the above-described details perature of from about 250 to about 350F.

2. A process as defined in claim 1 wherein said treated materials contain 75-100% of said emulsion based on the weight of said materials.

3. A process as defined in claim 1 wherein the dry weight of said graft copolymer on said materials after cure is about 2 to 4% by weight of said materials.

4. A process as defined in claim 1 wherein said treatment is carried out at temperatures ranging from about 100 to F.

normally susceptible to picking, snag and pull damage protected against such damage by treatment according to claim 1.

8. A material as defined in claim 7, selected from the group consisting of nylon, acrylics, polyester, cottonpolyester blends and rayon-polyester blends. 

1. A PROCESS COMPRISING TREATING TEXTILE MATERIALS CONTAINING THERMOPLASTI FIBERS AT A TEMPERATURE BETWEEN ABOUT 50*F AND ABOUT 125*F WITH AN AQUEOUS EMULSION CONTAINING APPROXIMATELY BY WEIGHT (1) 5 TO 15 OF A GRAFT COPOLMER CONTAINING APPROXIMATELY BY WEIGHT 0.1 TO 10% N-METHYLOL ACRYAMIDE AND 50 TO 70% OF C1-6 ALKYL ACRYLATE GRAFT POLYMERIZED ON 20 TO 40% OF A POLY (N-VINYL LACTAM) HAVING AN AVERAGE MOLECULAR WEIGHT BETWEEN ABOUT 40 AND ABOUT 2,000,000 AND HAVING THE FORMULA
 2. A process as defined in claim 1 wherein said treated materials contain 75-100% of said emulsion based on the weight of said materials.
 3. A process as defined in claim 1 wherein the dry weight of said graft copolymer on said materials after cure is about 2 to 4% by weight of said materials.
 4. A process as defined in claim 1 wherein said treatment is carried out at temperatures ranging from about 100* to 120*F.
 5. A process as defined in claim 1 wherein said curing is carried out at a temperature ranging from about 250* to 350*F for about 30 seconds to 2 minutes.
 6. A process as defined iN claim 1 wherein said C1 6 alkyl acrylate is selected from the group consisting of butyl acrylate and ethyl acrylate and hexyl.
 7. A thermoplastic fiber-containing textile material normally susceptible to picking, snag and pull damage protected against such damage by treatment according to claim
 1. 8. A material as defined in claim 7, selected from the group consisting of nylon, acrylics, polyester, cotton-polyester blends and rayon-polyester blends. 